What is it about?
This study provides a kinetic investigation into the thermal stability and decomposition behavior of 1,1-dihydroperoxycyclohexane (DHPC), a widely used gem-dihydroperoxide initiator and oxidant, across various organic solvents at 100–170 °C. Using 2-naphthol to inhibit induced radical chain reactions, we determined the first-order rate constants and activation parameters for DHPC. The study separated monomolecular peroxide decomposition from direct bimolecular reactions occurring between DHPC and oxidizable solvents.
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Why is it important?
Although 1,1-dihydroperoxycyclohexane is produced on an industrial scale (e.g., Cyclonox, Luperox) as a radical initiator, quantitative kinetic data regarding its thermal stability in organic solvents were previously lacking. Our findings show that DHPC is three orders of magnitude less thermally stable and significantly more reactive than tert-butyl hydroperoxide (t-BuOOH). Crucially, we demonstrated that DHPC not only undergoes homolytic O–O bond cleavage to yield free radicals, but also directly oxidizes surrounding solvent molecules. This knowledge allows chemists and engineers to model polymerization kinetics accurately and optimize safety parameters in industrial synthesis.
Perspectives
Filling the gap in fundamental kinetic data for industrially important peroxides is essential for safe and efficient chemical manufacturing. Discovering that DHPC actively participates in bimolecular reactions with solvents, rather than acting solely as a simple radical source, was a key insight of this work. We anticipate these kinetic parameters will help researchers better predict radical polymerization rates, select suitable inert solvents, and design safer, highly controlled chemical processes involving gem-dihydroperoxides.
Dr Stanislav A. Grabovskii
Ufa Institute of Chemistry of the RAS
Read the Original
This page is a summary of: Decomposition Kinetics of 1,1-Dihydroperoxycyclohexane in Some Organic
Solvents, Letters in Organic Chemistry, March 2023, Bentham Science Publishers,
DOI: 10.2174/1570178619666220727114411.
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